Epoxy group-containing copolymer and radiation sensitive resin compositions thereof

ABSTRACT

An epoxy group-containing thermosetting resin composition comprising (A) a copolymer obtained From (a) at least one member selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, (b) an epoxy group-containing unsaturated compound, (c) a monoolefin unsaturated compound, and optionally (d) a conjugated diolefin unsaturated compound, and (B) an organic solvent for dissolving the above copolymer. There is also provided another epoxy-group containing thermosetting resin composition which contains the above component (A), (C) a polymerizable compound having at least one ethylenically unsaturated double bond, and (D) a photopolymerization initiator. These epoxy-group containing thermosetting resin compositions are excellent in storage stability.

This is a Division, of application Ser. No. 08/094,436 filed on Jul. 21,1993, now U.S. Pat. No. 5,399,604.

The present invention relates to an epoxy group-containing resincomposition. More specifically, it relates to a one-pack type epoxygroup-containing thermosetting resin composition excellent in storagestability, and a radiation-sensitive resin composition containing anepoxy group-containing resin which composition permits facile removal ofan unnecessary portion with an alkaline developer after exposed.

Epoxy resin-based thermosetting resin compositions have been and areused for coating compositions, electric insulating materials, printedwiring boards, adhesives, civil construction materials, toolings,molding materials, sealing resins and protection films in a wide rangeof industries, since cured epoxy resin-based thermosetting resincompositions are excellent in heat resistance, mechanical properties,chemical resistance, adhesive properties, processability and opticalproperties.

Most of these conventional epoxy resin-based thermosetting resincompositions contain a special curing agent (a compound such as amine orcarboxylic acid) in combination for the purpose of promoting thecrosslinking reaction in heat treatment, since they can not be impartedwith sufficient properties (heat resistance and hardness) when an epoxyresin alone is heat-treated. One-pack type compositions containing anepoxy resin and a curing agent are poor in storage stability, andtwo-pack type compositions are therefore mainly used. When two-pack typecompositions are used, an epoxy resin and a curing agent are mixed justbefore use. Concerning the two-pack type compositions, however, thefollowing problems remain to solve. The procedure of mixing an epoxyresin with a curing agent is troublesome, it is difficult to adjust themixing ratio properly, and the composition is poor in storage stabilityafter the mixing of the two components.

For overcoming the above problems, a one-pack type thermosetting resincomposition containing a modified epoxy compound whose epoxy group hasbeen modified by a chemical reaction is being studied for development.However, problems still remain to solve concerning setting ofmodification reaction conditions for controlling by-products, andpurification and quantification of a reaction product for removingby-products.

On the other hand, radiation-sensitive compositions containing analkali-soluble resin such as a novolak resin permit the removal of anunnecessary portion in an exposure/development process, and they aretherefore widely used as materials for a bump-forming resist, a printedcircuit-forming resist, an interlayer insulating film and a circuitprotection film in producing a printed circuit board or mounting asemiconductor device and an electronic part on a printed circuit board;and as materials for a color filter protection film and a colored resistfor a color filter.

The defect with most of the above radiation-sensitive resin compositionscontaining an alkali-soluble resin such as a novolak resin is thatpatterns produced therefrom are inferior in physical properties such asheat resistance and solvent resistance since these compositions have nocrosslinking component.

For overcoming the above defect, it has been strongly desired to developa material having the properties of both an epoxy resin composition andan alkali-soluble resin, i.e., a resin composition which has boththermosetting properties (heat resistance) and photosensitivity, andstudies for the development are variously under way.

For example, an attempt is made to produce a material having theproperties of both radiation sensitivity and heat resistance bymodifying part of epoxy group of an epoxy oligomer with acrylic acid toproduce an epoxy acrylate having an epoxy group and a double bond andcombining the epoxy acrylate with a photopolymerization initiator.However, when the above epoxy acrylate is used as a base polymer, thereis a problem in terms of quality control that the modification ratio inthe modification reaction and the modification reaction are complicatedand that the quantification of the modification ratio is difficult.

When a resin having an epoxy group and an alkali-soluble resin aremixed, the compatibility of these two resins in the mixed resin solutionand the storage stability of the mixed resin solution remain to solve.

Further, studies on the development of materials having heat resistanceand photosensitivity such as photosensitive polyimide are also underway. However, there is a defect in that the solvent is limited to polarsolvents since polyimide is used.

When polyamic acid which is a precursor of polyimide is used, the bakingtemperature for imidation to impart heat resistance is required to be250° C. or higher, and it causes a problem of heat resistance(destruction) of various devices on a substrate during the process.Further, there is a defect in that the resultant coating is poor inhygroscopicity and transparency.

It is an object of the present invention to provide a novel epoxygroup-containing resin composition.

It is another object of the present invention to provide a novel epoxygroup-containing resin composition which undergoes facile curing underheat without any special curing agent, and gives a cured productexcellent in heat resistance, mechanical properties, chemicalresistance, adhesion, processability and optical properties.

It is further another object of the present invention to provide anepoxy group-containing thermosetting resin composition which hasexcellent storage stability as a one-pack type composition withoutimpairing the excellent properties of conventional epoxy resincompositions.

It is still further another object of the present invention to providean epoxy group-containing radiation-sensitive resin composition whichpermits facile removal of an unnecessary portion with an alkalideveloper solution after exposure.

It is yet another object of the present invention to provide an epoxygroup-containing thermosetting resin composition suitable as a materialfor a coating composition, an electrical insulating material, a printedcircuit board an adhesive, a civil construction material, toolings, amolding material and a protection film.

Further, it is another object of the present invention to provide anepoxy group-containing radiation-sensitive resin composition suitable asa material for a bump-forming resist, a circuit-forming resist, anelectric plating resist, an electroless plating resist, a solder resist,an etching resist, an interlayer insulating film, a gate insulatingfilm, a capacitor insulating film, a passivation film, an α-rayshielding film, and a buffer coating film which are required forproduction of a printed circuit board or for mounting semiconductors andelectronic parts on a printed circuit board; and as a material for acolor filter protection film for LCD, CCD and a spacer fir touch panelwhose optical properties are considered to be critical, a colored resistfor a color filter and a surface protection film for an optical disk.

Other objects and advantages of the present invention will be apparentfrom the following description.

According to the present invention, the above objects and advantages ofthe present invention are achieved by either of the following fourcompositions:

An epoxy group-containing thermosetting resin composition (to bereferred to as "first thermosetting resin composition" hereinafter)comprising;

(A) a copolymer (to be referred to as "first copolymer" hereinafter)obtained from the following unsaturated monomers (a), (b) and (c);

(a) at least one member selected from an unsaturated carboxylic acid andan unsaturated carboxylic acid anhydride,

(b) an epoxy group-containing unsaturated compound, and

(c) a monoolefin unsaturated compound, and

(B) an organic solvent for dissolving the above copolymer.

An epoxy group-containing thermosetting resin composition (to bereferred to as "second thermosetting resin composition" hereinafter)comprising;

(A)' a copolymer (to be referred to as "second copolymer" hereinafter)obtained from the following unsaturated monomers (a), (b), (c) and (d);

(a) at least one member selected from an unsaturated carboxylic acid andan unsaturated carboxylic acid anhydride,

(b) an epoxy group-containing unsaturated compound,

(c) a monoolefin unsaturated compound, and

(d) a conjugated diolefin unsaturated compound, and

(B) an organic solvent for dissolving the above copolymer.

An epoxy group-containing radiation-sensitive resin composition (to bereferred to as "first radiation-sensitive composition) comprising:

(A) the above first copolymer,

(C) a polymerizable compound having at least one ethylenicallyunsaturated double bond, and

(D) a photopolymerization initiator.

An epoxy group-containing radiation-sensitive resin composition (to bereferred to as "second radiation-sensitive composition" hereinafter)comprising:

(A)' the above second copolymer,

(C) a polymerizable compound having at least one ethylenicallyunsaturated double bond, and

(D) a photopolymerization initiator.

The compositions of the present invention have a principalcharacteristic feature in the use of a copolymer whose molecule haseither a carboxylic acid group or a carboxylic acid anhydride group andan epoxy group. This copolymer has solubility in an alkali, and it hasexcellent storage stability and undergoes facile curing under healwithout using any special curing agent. The compositions of the presentinvention give cured products excellent in heat resistance, mechanicalproperties, chemical resistance and optical properties.

The compositions of the present invention will be detailed hereinafter.

First copolymer

The first copolymer used in the present invention is a copolymerobtained from;

(a) at least one member selected from an unsaturated carboxylic acid andan unsaturated carboxylic acid anhydride,

(b) an epoxy group-containing unsaturated compound, and

(c) a monoolefin unsaturated compound.

The unsaturated carboxylic acid and the unsaturated carboxylic acidanhydride are preferably selected from aliphatic mono- and dicarboxylicacids having 3 to 5 carbon atoms, acid anhydrides thereof and halfesters of aliphatic dicarboxylic acids.

As the unsaturated carboxylic acid and the unsaturated carboxylic acidanhydride, more preferred are compounds of the formulae (1) and (2):##STR1## wherein each of R¹ and R² is independently a hydrogen atom or alower alkyl group having 1 to 6 carbon atoms. ##STR2##

wherein R¹ and R² are as defined above.

Examples of the unsaturated carboxylic acid and the unsaturatedcarboxylic acid anhydride preferably include unsaturated monocarboxylicacids such as acrylic acid, methacrylic acid and crotonic acid;unsaturated dicarboxylic acids such as maleic acid, fumaric acid,citraconic acid, mesaconic acid and iraconic acid; unsaturatedcarboxylic acid anhydrides such as maleic anhydride and iraconicanhydride; and unsaturated dicarboxylic acid monoalkyl esters such asmonomethyl fumarate, monobutyl fumarate, monomethyl maleate, monoethylmaleate, monobutyl maleate, monomethyl itaconate, monoethyl itaconateand monobutyl itaconate.

The above unsaturated carboxylic acid and unsaturated carboxylic acidanhydrides may be used alone or in combination.

The epoxy group-containing unsaturated compound (b) is preferably anepoxy alkyl ester of acrylic acid or α-alkylacrylic acid, andN-epoxyalkyl acrylamide or α-alkylacrylamide.

The epoxy group-containing unsaturated compound (b) is more preferably acompound of the formula (3), ##STR3##

wherein R³ is a hydrogen atom or a lower alkyl group having 1 to 4carbon atoms n is an integer of 1 to 10, and X is --O-- or a group ofthe formula ##STR4##

wherein R¹ is as defined above and m is an integer of 1 to 10.

Examples of the epoxy group-containing unsaturated compound includeglycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate,glycidyl α-n-propylacrylate, glycidyl butylacrylate, 3,4-epoxybutylacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate,6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethylacrylate,N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide andN-(4g-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide.

The above epoxy group-containing unsaturated compounds may be used aloneor in combination.

The monoolefin unsaturated compound (c) is selected fromradical-polymerizable monoolefins other than the above compounds (a) and(b). The monoolefin unsaturated compound (c) preferably includes alkylester, hydroxyalkyl ester, cycloalkyl ester or aryl ester of aliphaticunsaturated monocarboxylic acid, dialkyl ester of aliphatic unsaturateddicarboxylic acid, and other vinyl compound.

The monoolefin unsaturated compound (c) is more preferably selected fromcompounds of the formulae (4) and (5): ##STR5##

wherein R⁴ is a hydrogen atom or a lower alkyl group having 1 to 4carbon atoms, and R⁵ is a hydrogen atom, a lower alkyl group having 1 to4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms.##STR6##

wherein each of R⁶ and R⁷ is independently a hydrogen atom or methylgroup, and R⁸ is an alkyl group having 1 to 6 carbon atoms or acycloalkyl group having 5 to 12 carbon atoms provided that thecycloalkyl group is optionally substituted.

Examples of the monoolefin unsaturated compound (c) include alkylmethacrylates such as methyl methacrylate, ethyl methacrylate, n-butylmethacrylate, sec-butyl methacrylate and tert-butyl methacrylate; alkylacrylates such as methyl acrylate and isopropyl acrylate; cycloalkylmethacrylates such as cyclohexyl methacrylate, 2-methylcyclohexylmethacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethylmethacrylate and isopropyl methacrylate; cycloalkyl acrylates such ascyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanylacrylate, dicyclopentanyloxyethyl acrylate and isopropyl acrylate; arylmethacrylates such as phenyl methacrylate and benzyl methacrylate; arylacrylates such as phenyl acrylate and benzyl acrylate; dicarboxylic aciddiesters such as diethyl maleate, diethyl fumarate and diethylitaconate; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and2-hydroxypropyl methacrylate; styrene, α-methylstyrene, m-methylstyrene,p-methylstyrene, vinyltoluene, p-methoxystyrene andp-tert-butoxystyrene.

The above compounds may be used alone or in combination.

The first copolymer (A) is composed of structural units derived from theabove unsaturated monomers. Above all, preferred are structural units ofthe formulae (1)-a, (2)-a, (3)-a, (4)-a and (5)-a. ##STR7##

wherein R¹ and R² are as defined in the formula (1). ##STR8##

wherein R¹ and R² are as defined in the formula (2). ##STR9##

wherein R³, X and n are as defined in the formula (3). ##STR10##

wherein R⁴ and R⁵ are as defined in the formula (4). ##STR11##

wherein R⁶, R⁷ and R⁸ are as defined in the formula (5).

Second copolymer (A)'

The second copolymer (A)' used in the present invention is a copolymerobtained from compounds (a), (b) and (c) which are the same as thecompounds (a), (b) and (c) described regarding the first copolymer (A)and a conjugated diolefin unsaturated compound (d).

As the conjugated diolefin compounds, for example, preferred is acompound of the formula (6), ##STR12##

wherein each of R⁹ and R¹⁰ is independently a hydrogen atom, a methylgroup or an optionally substituted phenyl group.

Examples of the conjugated diene unsaturated compound (6) include1,3-butadiene, isoprene and 2,3-dimethylbutadiene.

It should be understood that the descriptions concerning the compounds(a), (b) and (c) for the first copolymer (A) can be applied to thecompounds (a), (b) and (c) for the second copolymer (A)'.

The second copolymer (A)' is composed of structural units derived fromthe above unsaturated monomers. Preferred are the structural units ofthe already described formulae (1)-a, (2)-a, (3)-a, (4)-a and (5)-a andthe structural unit of the formula (6)-a: ##STR13##

wherein R⁹ and R¹⁰ are as defined in the formula (6).

The second copolymer is preferably composed of the structural units ofthe formulae (1), (3), (4), (5) and (6) or the structural units of theformulae (2), (3), (4), (5) and (6).

The copolymer (A) or (A)' used in the present invention containspreferably 5 to 40% by weight, more preferably 10 to 30% by weight, ofstructural units derived from at least one of the above unsaturatedcarboxylic acid and unsaturated carboxylic acid anhydride (a).

The copolymer (A) or (A)' used in the present invention containspreferably 10 to 70% by weight, more preferably 20 to 60% by weight, ofstructural units derived from the above epoxy group-containingunsaturated compound (b).

The copolymer (A) or (A)' used in the present invention containspreferably 10 to 70% by weight, more preferably 20 to 60% by weight, ofstructural units derived from the above monoolefin compound (c).

The copolymer (A)' used in the present invention contains preferably 0.1to 30% by weight, more preferably 1 to 15% by weight, of structuralunits derived from the above conjugated diolefin compound (d).

As described above, the copolymer (A) used in the present invention isobtained by copolymerizing at least one of the above unsaturatedcarboxylic acid and unsaturated carboxylic acid anhydride (a), the aboveepoxy group-containing unsaturated compound (b) and the above monoolefinunsaturated compound (c). The copolymer (A)' used in the presentinvention is obtained by copolymerizing at least one of the aboveunsaturated carboxylic acid and unsaturated carboxylic acid anhydride(a), the above epoxy group-containing unsaturated compound (b), theabove monoolefin unsaturated compound (c) and the above conjugateddiolefin unsaturated compound (d). Therefore, the gelation of thepolymerization system in the polymerization can be prevented, and thecopolymer (A) and the copolymer (A)' are excellent in storage stability.

Meanwhile, in producing a base polymer only From either the unsaturatedcarboxylic acid or unsaturated carboxylic acid anhydride (a) and theepoxy group-containing unsaturated compound (b), the epoxy group and thecarboxylic acid group are liable to react with each other and crosslinkto cause gelation of the reaction system.

The thermosetting resin composition and the radiation-sensitive resincomposition which contain the above copolymer (A) or (A)' can form acured film excellent in heat resistance.

When the amount of the structural units derived from the epoxygroup-containing unsaturated compound (b) is less than 10% by weight orwhen the amount of the structural units derived from the monoolefinunsaturated compound (c) is more than 70% by weight, the heat resistanceof a cured film obtained from the thermosetting resin composition or theradiation-sensitive resin composition containing the copolymer (A) or(A)' is sometimes insufficient.

The thermosetting resin composition and the radiation-sensitive resincomposition which contain the copolymer (A)' containing structural unitsderived from the conjugated diolefin unsaturated compound (d) in theabove amount range can highly flatten a height difference of a substrateand can highly improve the sensitivity to radiation.

When the copolymer (A)' contains more than 30% by weight of structuralunits derived from the conjugated diolefin unsaturated compound (d), theheat resistance of a cured film obtained from the thermosetting resincomposition or the radiation-sensitive resin composition containing thecopolymer (A)' is sometimes insufficient.

The above copolymers (A) and (A)' are soluble in an alkaline aqueoussolution.

The above copolymers (A) and (A)' require no modification step, andthese copolymers can be produced by a copolymerization step alone. Thecopolymer (A) can be obtained by radical-polymerizing at least one ofthe above unsaturated carboxylic acid and unsaturated carboxylic acidanhydride (a), the above epoxy group-containing unsaturated compound (b)and the above monoolefin unsaturated compound (c), and the copolymer(A)' can be obtained by radical-polymerizing at least one of the aboveunsaturated carboxylic acid and unsaturated carboxylic acid anhydride(a), the above epoxy group-containing unsaturated compound (b), theabove monoolefin unsaturated compound (c) and the above conjugateddiolefin unsaturated compound (d), in a solvent in the presence of acatalyst (polymerization initiator).

The above solvent is selected from alcohols such as methanol andethanol; ethers such as tetrahydrofuran; cellosolve esters such asmethyl cellosolve acetate; other aromatic hydrocarbons; ketones; andesters.

The catalyst for the radical polymerization is selected from usualradical polymerization initiators. Examples of the catalyst include azocompounds such as 2,2'-azobisisobutyronitrile,2,2'-azobis(2,4-dimethylvaleronitrile) and2,2'-azobis(4-methoxy-2,4-dimethylvaleronltrile); organic peroxides suchas benzoyl peroxide, lauroyl peroxide, tertbutylperoxypivalate and1,1'-bis-(tertbutylperoxy)cyclohexane; and hydrogen peroxide. When aperoxide is used as a radical polymerization initiator, a combination ofthe peroxide with a reducing agent may be used as a redox initiator.

The above copolymers (A) and (A)' are not specially limited in molecularweight and molecular distribution as far as solutions of thecompositions of the present invention can be uniformly applied.

[B] Organic solvent

The organic solvent used in the present invention serves to form asolution of the above copolymer (A) or (A)', and is selected from thosewhich are compatible and unreactive with the copolymers (A) or (A)'. Theorganic solvent includes alcohols such as methanol and ethanol, etherssuch as dichloroethyl ether, n-butyl ether, diisoamyl ether,methylphenyl ether and tetrahydrofuran; glycol ethers such as ethyleneglycol monomethyl ether and ethylene glycol monoethyl ether: cellosolveacetates such as methyl cellosolve acetate, ethyl cellosolve acetate anddiethyl cellosolve acetate; carbitols such as methyl ethyl carbitol,diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, diethylene glycol dimethyl ether, diethylene glycolmethylethyl ether and diethylene glycol diethyl ether; propylene glycolalkyl ether acetates such as propylene glycol methyl ether acetate andpropylene glycol propyl ether acetate; aromatic hydrocarbons such astoluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone,4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone,methyl-n-butylketone, methyl-n-amylketone and 2-heptanone; saturatedaliphatic monocarboxylic acid alkyl esters such as ethyl acetate,n-butyl acetate and isobutyl acetate; lactates such as methyl lactateand ethyl lactate; alkyl oxyacetates such as methyl oxyacetate, ethyloxyacetate and butyl oxyacetate; alkyl alkoxyacetates such as methylmethoxyacetate, ethyl methoxyacetate, butyl methoxyacetate,methylethoxyacetate and ethyl ethoxyacetate; alkyl 3-oxypropionates suchas methyl 3-oxyproplonate and ethyl 3-oxyproplonate: alkyl3-alkoxyproplonates such as methyl 3-methoxyproplonate, ethyl3-methoxyropionate, ethyl 3-ethoxypropionate and methyl3-ethoxypropionate; alkyl 2-oxypropionates such as methyl2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; alkyl2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl2-methoxypropionate, ethyl 2-ethoxypropionate and methyl2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; alkylmonooxymonocarboxylates of alkyl 2-alkoxy-2-methyl propionates such asmethyl 2-methoxy-2-methylpropionate and ethyl2-ethoxy-2methylpropionate: esters such as ethyl 2hydroxypropionate,ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl2-hydroxy-3-methylbutanoate; ketonic acid esters such as ethyl pyruvate;and high-boiling solvents such as N-methylformamide,N,N-dimethylformamide, N-methylformanilide, N-methylacetamide,N,N-dimethylacetamide, N-methylpyrrolldone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid,caprilic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate,ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone,ethylene carbonate, propylene carbonate and phenylcellosolve acetate.

In view of compatibility and reactivity, preferred are glycol etherssuch as ethylene glycol monoethyl ether; ethylene glycol alkyl etheracetates such as ethylcellosolve acetate; esters such as ethyl2-hydroxypropionate; and diethylene glycols such as diethylene glycolmonomethyl ether.

The first thermosetting resin composition of the present inventioncomprises the above first copolymer (A) and the above organic solvent(B). The second thermosetting resin composition of the present inventioncomprises the second copolymer (A)' and the organic solvent (B).

In these first and second thermosetting resin compositions, the amountof the copolymer (A) or (A)' based on the total amount of thecorresponding composition is 1 to 70% by weight, more preferably 8 to50% by weight.

[C] Polymerizable compound

The polymerizable compound (C) having at least one ethylenicallyunsaturated double bond, used in the present invention, is preferablyselected from monofunctional or polyfunctional esters of acrylic acid ormethacrylic acids.

Examples of the monofunctional (meth)acrylates include commerciallyavailable products such as Aronix M-101, M-111 and M-114 (supplied byToagosel Chemical Industry Co., Inc.), AKAYARAD TC-110S and TC-110S(supplied by Nippon Kayaku Co. Ltd), and V-158 and V-2311 (supplied byOsaka Organic Chemical Industry Ltd). Examples of the difunctional(meth)acrylates include commercially available products such as AronixM-210, M-240 and M-6200 (supplied by Toagosei Chemical Industry Co.,Inc.), KAYARAD HDDA, HX-220 and R-604 (supplied by Nippon Kayaku Co.,Ltd), V260, V313 and V335P (supplied by Osaka Organic Chemical IndustryLtd.) and Furuorenhydroxy acrylate (ASF-400 supplied by Nippon SteelChemical Co., Ltd.). Examples of the trifunctional or higher(meth)acrylates include trimethylolpropane triacrylate, pentaerythritoltriacrylate, trisacryloyloxyethyl phosphate, pentaerythritoltetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate, and examples of their commercial products include AronixM-309, M-400, M-40S, M-450, M-7100, M-8080 and M-8060 (supplied byToagosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, DPCA-20, DPCA-30,DPCA- 60 and DPCA-120 (supplied by Nippon Kayaku Co., Ltd.) and V-295,V-300, V-360, V-GPT, V-3PA and V-400 (supplied by Osaka Organic ChemicalIndustry, Ltd).

The above compounds may be used alone or in combination. The amount ofthe polymerizable compound (C) per 100 parts by weight of the copolymer(A) or (A)' is preferably 40 to 200 parts by weight, more preferably 50to 150 parts by weight. When this amount is less than 40% by weight. Thesensitivity in oxygen atmosphere is liable to deteriorate. When itexceeds 200 parts by weight, the compatibility with the copolymer (A) or(A)' is liable to deteriorate and a formed coating is liable to have atoughened surface.

(D) Photopolymerization initiator

The photopolymerization initiator (D) used in the radiation-sensitiveresin composition of the present invention is selected from photoradical polymerization initiators and photo cationic polymerizationinitiators.

In using the photopolymerization initiator, it is necessary to considerexposure conditions (whether the exposure is carried out in oxygenatmosphere or it is carried out In oxygen-free atmosphere).Specifically, when the exposure is carried out in oxygen-freeatmosphere, the photopolymerization initiator can be selected fromalmost all of general photo radical polymerization initiators and photocationic polymerization initiators.

Examples of the photo radical polymerization initiators includeα-diketones such as benzyl and diacetyl; acyloins such as benzoin;acyloin ethers such as benzoin methyl ether, benzoin ethyl ether andbenzoin isopropyl ether; benzophenones such as thioxanthone,2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone,4,4'-bis(dimethylamino)benzophenone and4,4'-bis(diethylamino)benzophenone; acetophenones such as acetophenone,p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone,2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone,2-methyl[4(methylthio)phenyl]-2-morpholino-1-propane and2-benzyl-2-diemthylamino-1-(4-morpholinophenyl)-butan-1-one; quinonessuch as anthraquinone and 1,4-naphthoquinone; halogen compounds such asphenacyl chloride, tribromomethylphenylsulfone andtris(trichloromethyl)-s-triazine; peroxides such as di-tert-butylperoxide; and acylphosphine oxides such as2,4,6-trimethylbenzoyldlpehnylphosphine oxide.

The photo cationic polymerization initiator can be selected from thefollowing commercially available products such as Adeca Ultraset PP-33(supplied by Asahi Denka Kogyo K.K.) which is diazonium salt, OPTOMERSP-150, 170 (supplied by Asahi Denka Kogyo K.K.) which is sulfonium saltand IRGACURE 261 (supplied by Ciba Geigy) which is a metallocenecompound.

When the exposure is carried out in oxygen atmosphere, some of the photoradical polymerization initiators undergo Inactivation (decrease insensitivity) due to oxygen, and a formed film is sometimes insufficientin a resin remaining ratio and hardness of an exposed portion. When theexposure is carried out in oxygen atmosphere, preferred are (a) all ofthe above photo cationic polymerization initiators (which are almostfree from inactivation of active species by oxygen) and (2) some of thephoto radical polymerization initiators, e.g., acetophenones such as2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane and2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butan-1-one, halogencompounds such as phenacyl chloride, tribromomethylphenylsulfone andtris(trichloromethyl)-s-triazine, and acylphosphine oxides such as2,4,6-trimethylbenzoyldlphenylphosphine oxide. The amount of thephotopolymerization initiator per 100 parts by weight of the copolymer(A) or (A)' is preferably 1.0 to 50 parts by weight, more preferably 5to 30 parts by weight. When this amount is less than 1 by weight, theinactivation of radical (decrease in sensitivity) is liable to occur dueto oxygen. When it exceeds 50 pares by weight, the color density in thesolution is sometimes high.

Further, the inactivation by oxygen can be decreased and the highsensitivity can be achieved, by using the photo radical polymerizationinitiator and either the photo cationic polymerization initiator or aphotosensitizer in combination.

Other additives

Surfactant

The thermosetting resin composition and radiation-sensitive resincomposition of the present invention may contain a surfactant. Examplesof the surfactant include commercially available fluorine-containingsurfactants such as BM-1000 and BM-1100 (supplied by BM Chemie), MegafacF142D, F172, F173 and F183 (supplied by Dainippon Ink & Chemicals,Fluorad FC-135, FC-170C, FC-430 and FC-431 (supplied by Sumitomo 3M Co.,Ltd.), Surflon S-112, S-113, S-131, S-141 and S-145 (supplied by AsahiGlass Co., Ltd.) and SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428(supplied by Toray Dow Corning Silicone). The amount of the surfactantper 100 parts by weight of the copolymer (A) or (A)' is preferably 5% byweight or less, more preferably 0.01 to 2% by weight.

Adhesive aid

The thermosetting resin composition and radiation-sensitive resincomposition of the present invention may contain an adhesive aid forimproving the adhesion of each composition to a substrate. A functionalsilane coupling agent is effective as the adhesive aid. The functionalsilane coupling agent refers to a silane coupling agent having areactive substituent such as a carboxyl group, a methacryloyl group, anisocyanate group or an epoxy group. Specific examples of the functionalsilane coupling agent include trimethoxysilylbenzoic acid,γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane,vinylerimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane andβ-(3,4-epoxycylcohexyl)ethyltrimethoxysilane. These adhesive aids may beused alone or in combination. The amount of the adhesive aid per 100parts by weight of the copolymer (A) or (A)' is preferably 20 parts byweight or less, more preferably 10 parts by weight or less.

Method of use of thermosetting resin composition

Method of forming coating

When the thermosetting resin composition of the present invention isused, a coating can be formed by applying a solution of thethermosetting resin composition to a predetermined substrate surface andheating the composition. The method for the application to a substratesurface is not specially limited, and includes a spraying method, a rollcoating method, a spin coating method, a screen printing method and anapplicator method.

The composition of the present invention gives a coating excellent inheat resistance, transparency and hardness by heating it by means of aheating device such as a hot plate or an oven at a predeterminedtemperature, e.g., between 120° and 280° C., for a predetermined periodof time, e.g., for 5 to 30 minutes on a hot plate or for 30 to 90minutes in an oven.

Method of use of radiation-sensitive resin composition

1. Method of forming coating

When the radiation-sensitive resin composition of the present inventionis used, an intended coating can be formed by applying a solution of theradiation-sensitive resin composition to a predetermined substratesurface and removing the solvent by preliminary heating. The method ofthe application to a substrate is not specially limited, and includes aspin coating method, a roll coating method, a screen printing method andan applicator method.

The conditions for drying a coating of the composition of the presentinvention differs depending upon the kinds of components of thecomposition, the proportions of the components and the thickness of thecoating, while the coating is generally dried at 70° to 90° C. for 1 to10 minutes. When it is dried for too short a time, the state of adhesionintimacy is poor in development. When it is dried for too long a time,the resolution deteriorates due to heat exposure.

2. Method of exposure

The above-obtained coating is exposed to 200 to 500 nm ultraviolet lightor visible light through a predetermined pattern mask, whereby anecessary portion alone can be photo-cured. The light source of theseactinic radiations includes a low-pressure mercury lamp, a high-pressuremercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lampand an argon laser. Further, X-ray and electron beam can be used asactive energy radiation.

The exposure dose differs depending upon the kinds of components of eachcomposition, amounts thereof and the thickness of dried coating. When ahigh-pressure mercury lamp is used, the exposure dose is 500 mJ/cm² orless (by means of a 865 nm sensor).

3. Method of development

After the above exposure is carried out, there is employed a developmentmethod in which an alkaline aqueous solution is used as a developersolution and an unnecessary portion is dissolved and removed with thedeveloper solution whereby a necessary portion alone is retained to forma pattern. Examples of the developer solution include aqueous solutionsof alkalis such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium hydrogencarbonate, sodium silicate, sodiummetasillcate, aqueous ammonia. ethylamine, n-propylamine, diethylamine,di-n-propylamine. triethylamine, methyldiethylamine,dimethylethanolamine, triethanolamine, tetramethylammonlum hydroxide,tetraethylammonium hydroxide, pyrrole, piperidine,1,8-diazabicyclo[5,4,0]-7-undecene and 1,5-diazabicyclo[4,3,0]-5-nane.The developer solution may a mixture of an aqueous solution of any oneof the above alkalis with a proper amount of a water-soluble organicsolvent such as methanol or ethanol or a surfactant.

The development time differs depending upon the kinds of components ofthe composition, the proportions thereof and the thickness of a driedcoating, while it is generally 30 to 180 seconds. The development methodincludes a dipping method, a puddling method and a spraying method.After the development, the coating is washed with flowing water for 30to 90 seconds and air-dried with an air gun or dried in an oven toobtain an intended pattern.

4. Post-treatment

The composition of the present invention can be sufficiently cured byexposing it to the above actinic light or energy ray, while it may befurther subjected to exposure (to be sometimes referred to"post-exposure" hereinafter) or heat-cured. The post-exposure orheat-curing is preferred particularly for obtaining a permanent coating.The post-exposure can be carried out by the same method as above, andthe exposure dose is not specially limited. When a high-pressure mercurylamp is used, however, the exposure dose is preferably 1,000 mJ/cm² orless (by means of a 365 nm sensor). The heat-curing can be carried outby heating the coating by means of a heating device such as a hot plateor an oven at a predetermined temperature. e.g., between 120° and 250°C. for a predetermined period of time, e.g., for 10 to 60 minutes on ahot plate or for 30 to 90 minutes in an oven. As a result, there can beobtained a cured product having further excellent properties.

As explained above, it has been found by the present inventors that theexcellent properties of an epoxy resin and an alkali-soluble resin canbe retained together by means of copolymerization differing fromconventional modification and mixing methods. As a result, it has beenmade possible to obtain a one-pack type thermosetting resin compositionexcellent in storage stability. Further, the copolymers are soluble inan alkali, and when mixed with a radiation-sensitive component,therefore, there can be obtained a radiation-sensitive resin compositionwhich permits facile removal of an unnecessary portion by development.Furthermore, the composition can be imparted with properties such aschemical resistance, intimate adhesion and resistance to soldering asrequired by controlling the degree of heat crosslinkage thereof. Theabove composition can be suitably used as a coating composition, anelectric insulating material, a printed circuit board, an adhesive, acivil construction material, toolings, a molding material and aprotection film for which an epoxy resin has been conventionally used,and further, the above composition can be also used as a bump-formingresist, a wiring-forming resist, an electric plating resist, anelectroless plating resist, a solder resist, an etching resist, aninterlayer insulating film, a gate insulating film, a capacitorinsulating film, a passivation film, an α-ray shielding film, and abuffer coating film which are required for production of a printedcircuit board or for mounting semiconductors and electronic parts on aprinted circuit board, where alkali-soluble resins are used; and as acolor filter protection film for LCD and CCD whose optical propertiesare considered to be critical, a colored resist for a color filter and asurface protection film for an optical disk.

The composition of the present invention can be also used as a solderresist and an etching resist.

The present invention will be more specifically explained with referenceto Examples. However, the present invention shall not be limited bythese Examples. In Examples, "%" stands for "% by weight" unlessotherwise specified.

Synthesis Example 1

A separable flask equipped with a stirrer, a cooling tube, a nitrogenintroducing tube, a thermometer and a dry ice/methanol reflux device wascharged with:

    ______________________________________                                        dicyclopentanyl methacrylate                                                                       57.0       g                                             methacrylic acid     33.0       g                                             glycidyl methacrylate                                                                              60.0       g                                             2,2'-azobisisobutyronitrile                                                                        6.0        g                                             and                                                                           diethylene glycol dimethyl ether                                                                   450.0      g.                                            ______________________________________                                    

The separable flask was flushed with nitrogen for 30 minutes and, andthen was immersed in an oil bath. While the mixture was stirred, thepolymerization was carried out for 5 hours at the reaction temperaturekept at 80° C. to give a resin solution having a solid content of 25.8%by weight, and the polymerization conversion was about 100%.

The above-obtained resin solution is referred to as "Resin solution 1"hereinafter.

Synthesis Example 2

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 2" hereinafter.

    ______________________________________                                        sec-butyl methacrylate 65.0 g                                                 methacrylic acid       20.0 g                                                 glycidyl methacrylate  65.0 g                                                 2,2'-azobis(2,4-dimethylvaleronitrile)                                                               6.0 g                                                  and                                                                           dioxane                450.0 g                                                ______________________________________                                    

Synthesis Example 3

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.7% by weight. Thisresin solution is referred to as "Resin solution 3" hereinafter.

    ______________________________________                                        styrene                15.0 g                                                 dicyclopentanyl methacrylate                                                                         45.0 g                                                 methacrylic acid       30.0 g                                                 glycidyl methacrylate  60.0 g                                                 2,2'-azobis(2,4-dimethylvaleronitrile)                                                               6.0 g                                                  and                                                                           diethylene glycol dimethyl ether                                                                     450.0 g                                                ______________________________________                                    

Synthesis Example 4

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution Is referred to as "Resin solution 4" hereinafter.

    ______________________________________                                        methyl methacrylate    37.5 g                                                 methacrylic acid       37.5 g                                                 3,4-epoxybutylglycidyl methacrylate                                                                  75.0 g                                                 2,2'-azobisisobutyronitrile                                                                          6.0 g                                                  and                                                                           diethylene glycol dimethyl ether                                                                     450.0 g                                                ______________________________________                                    

Synthesis Example 5

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 5" hereinafter.

    ______________________________________                                        benzyl methacrylate     61.0 g                                                maleic anhydride        40.0 g                                                6,7-epoxyheptylglycidyl α-ethylacrylate                                                         49.0 g                                                2,2'-azobis-2,4-dimethylvaleronitrile                                                                 6.0 g                                                 and                                                                           dioxane                 450.0 g                                               ______________________________________                                    

Synthesis Example 6

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 6" hereinafter.

    ______________________________________                                        1,3-butadiene            4.5 g                                                styrene                  15.0 g                                               dicyclopentanyl methacrylate                                                                           40.5 g                                               methacrylic acid         30.0 g                                               glycidyl methacrylate    60.0 g                                               2,2'-azobisisobutyronitrile                                                                            6.0 g                                                and                                                                           diethylene glycol dimethyl ether                                                                       450.0 g                                              ______________________________________                                    

Synthesis Example 7

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.6% by weight. Thisresin solution is referred to as "Resin solution 7" hereinafter.

    ______________________________________                                        1,3-butadiene            15.0 g                                               styrene                  15.0 g                                               dicyclopentanyl methacrylate                                                                           37.5 g                                               methacrylic acid         22.5 g                                               glycidyl methacrylate    60.0 g                                               2,2'-azobisisobutyronitrile                                                                            6.0 g                                                and                                                                           diethylene glycol dimethyl ether                                                                       450.0 g                                              ______________________________________                                    

Synthesis Example 8

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.8% by weight. Thisresin solution is referred to as "Resin solution 8" hereinafter.

    ______________________________________                                        1,3-butadiene           10.0 g                                                styrene                 15.0 g                                                dicyclopentanyl methacrylate                                                                          35.0 g                                                itaconic acid           35.0 g                                                6,7-epoxyheptylglycidyl α-ethylacrylate                                                         55.0 g                                                benzoyl peroxide        6.0 g                                                 and                                                                           diethylene glycol monomethyl ether                                                                    450.0 g                                               ______________________________________                                    

Synthesis Example 9

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 9" hereinafter.

    ______________________________________                                        1,3-butadiene       15.0 g                                                    styrene             15.0 g                                                    dicyclopentanyl methacrylate                                                                      37.5 g                                                    maleic anhydride    22.5 g                                                    glycidyl methacrylate                                                                             60.0 g                                                    2,2'-azobisisobutyronitrile                                                                       6.0 g                                                     and                                                                           methyl 3-methoxypropionate                                                                        450.0 g                                                   ______________________________________                                    

Synthesis Example 10

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 10" hereinafter.

    ______________________________________                                        1,3-butadiene          15.0 g                                                 p-methoxystyrene       20.0 g                                                 2-methylcyclohexyl acrylate                                                                          15.0 g                                                 methacrylic acid       35.0 g                                                 6,7-epoxyheptylglycidyl methacrylate                                                                 65.0 g                                                 2,2'-azobisisobutyronitrile                                                                          6.0 g                                                  and                                                                           diethylene glycol dimethyl ether                                                                     450.0 g                                                ______________________________________                                    

Synthesis Example 11

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 11" hereinafter.

    ______________________________________                                        isoprene               7.5 g                                                  styrene                22.5 g                                                 methyl methacrylate    12.5 g                                                 itaconic acid          27.5 g                                                 glycidyl methacrylate  80.0 g                                                 benzoyl peroxide       6.0 g                                                  and                                                                           diethylene glycol monomethyl ether                                                                   450.0 g                                                ______________________________________                                    

Synthesis Example 12

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.7% by weight. Thisresin solution is referred to as "Resin solution 12" hereinafter.

    ______________________________________                                        1,3-butadiene         20.0 g                                                  styrene               50.0 g                                                  dicyclopentanyl methacrylate                                                                        45.0 g                                                  methacrylic acid      35.0 g                                                  2,2'-azobisisobutyronitrile                                                                         6.0 g                                                   and                                                                           diethylene glycol dimethyl ether                                                                    450.0 g                                                 ______________________________________                                    

Synthesis Example 13

The polymerization was carried out in the same manner as in SynthesisExample 1 except that the charged compounds were changed as follows, togive a resin solution having a solid content of 25.9% by weight. Thisresin solution is referred to as "Resin solution 13" hereinafter.

    ______________________________________                                        1,3-butadiene         15.0 g                                                  styrene               15.0 g                                                  dicyclopentanyl methacrylate                                                                        40.0 g                                                  glycidyl methacrylate 80.0 g                                                  2,2'-azobisisobutyronitrile                                                                         6.0 g                                                   and                                                                           diethylene glycol dimethyl ether                                                                    450.0 g                                                 ______________________________________                                    

Example 1

(1) Preparation of thermosetting resin composition

γ-Methacryloxypropyltrimethoxysil in an amount of 10 parts by weightbased on the resin content of Resin solution 1 obtained in SynthesisExample 1 ("part by weight" is used in this sense hereinafter in thisExample) and 0.1 part by weight of SH-28PA were added to 100 g of Resinsolution 1 obtained in Synthesis Example 1, and these components weremixed. The mixture was filtered with a 0.22 μm millipore filter to givea composition solution (1).

(2) Formation of coating

The above composition solution (1) was applied to an SiO₂ glasssubstrate with a spinner, and applied composition solution washeat-treated on a hot plate at 180° C. for 80 minutes to give a coatinghaving a thickness of 2.0 μm.

(8) Evaluation of transparency

A coating was formed in the same manner as in the above (2) except thatthe SiO₂ glass substrate was replaced with a Corning 7059 (supplied byCorning).

The above-obtained coating was measured for a transmittance at 400 to800 nm with a spectrophotometer (model 150-20, double beam, supplied byHitachi Ltd.). The transparency was evaluated as follows. When thelowest transmittance was over 98%, a coating was rated as A. When it was95 to 98%, a coating was rated as B. When it was less than 95%, acoating was rated as X. Table 1 shows the result.

(4) Evaluation of heat resistance

A substrate on which a coating had been formed in the same manner as inthe above (2) was heated on a hot plate at 250° C. for 1 hour, and thenthe coating was measured for a thickness. Then, the film remaining ratioto the thickness of the coating before the heat treatment wascalculated. The heat resistance was evaluated as follows. When the filmremaining ratio was over 98%, a coating was rated as A. When it was 95to 98%, a coating was rated as B. When it was less than 95%, a coatingwas rated as X. Table 1 shows the result.

(5) Evaluation of resistance to discoloration under heat

A substrate on which a coating had been formed in the same manner as inthe above (2) was heated on a hot plate at 250° C. for 1 hour. Then, thecoating was measured for a transmittance with a spectrophotometer in thesame manner as in the above 3), and the change ratio to thetransmittance of the coating before the heat treatment was calculated.The resistance to discoloration under heat was evaluated as follows.When the change ratio was less than 5%, a coating was rated as A. Whenit was 5 to 10%, a coating was rated as B. When it was over 10%, coatingwas rated as X. Table 1 shows the result.

(6) Measurement of hardness

The same coating as that prepared in the above (2) was measured for ahardness by a pencil scratch test according to JIS K-5400-1990, 8.4.1.The hardness was evaluated on the basis of scratch on the coating. Table1 shows the result.

(7) Evaluation of flattening

A coating was formed in the same manner as in the above (2) except thatthe SiO₂ glass substrate used in the above (1) was replaced with an SiO₂wafer having a height difference on the surface by 1.0 μm. Then, thesubstrate was measured for a height difference on the surface with atracer type film thickness measuring apparatus.

(8) Adhesion test

A coating formed in the above (2) was subjected to a tape peel testaccording to JIS D-0202, and the adhesion was evaluated as follows. Whenthe peel was less than 2%, a coating was rated as A. When it was 2 to 5%, a coating was rated as B. When it was over 5%, a coating was rated asX. Table 1 shows the result.

(9) Storage stability

The composition solution (1) obtained in the above (1) was heated in aconstant-temperature constant-humidity device at 40° C. for 200 hours,and measured for a viscosity change. The storage stability was evaluatedas follows. When the viscosity change was less than 5%, a solution wasrated as A. When it was 5 to 10% a solution was rated as B When it wasover 10 %, a solution was rated as X. Table 1 shows the result.

Examples 2-11

Composition solutions were prepared in the same manner as in Example 1except that Resin solution was replaced with Resin solutions 2 to 11obtained in Synthesis Examples 2 to 11. The composition solutions weretreated and evaluated in the same manner as in Example 1.

Table 1 shows the results.

                                      TABLE 1                                     __________________________________________________________________________                          Resistance to                                                            Heat discoloration                                                                        Flattening                                                                          Adhesion                                                                           Storage                               Example                                                                            Hardness                                                                           Transparency                                                                         resistance                                                                         under heat                                                                           μm test stability                             __________________________________________________________________________    1    6H   A      A    A      0.2>  A    A                                     2    5H   A      A    A      0.2>  A    A                                     3    5H   A      A    A      0.3>  A    A                                     4    5H   A      A    A      0.3>  A    A                                     5    5H   A      A    A      0.2>  A    A                                     6    4H   A      A    A      0.1>  A    A                                     7    4H   A      A    A      0.1>  A    A                                     8    6H   A      A    A      0.1>  A    A                                     9    6H   A      A    A      0.1>  A    A                                     10   4H   A      A    A      0.1>  A    A                                     11   5H   A      A    A      0.1>  A    A                                     __________________________________________________________________________

Comparative Examples 1-2

Composition solutions were prepared in the same manner as in Example 1except that Resin solution 1 was replaced with Resin solutions 12 and 13obtained in Synthesis Examples 12 to 13. The composition solutions weretreated and evaluated in the same manner as in Example 1.

Table 2 shows the results.

Comparative Example 3

An attempt was made to prepare a composition solution in the same manneras in Example 1 except that Resin solution 1 obtained in SynthesisExample 1 was replaced with a resin solution prepared by mixing Resinsolutions 12 and 13 obtained in Synthesis Examples 12 and 13 in a solidcontent mixing ratio of 2:1. However, Resin solutions 12 and 13 had toopoor compatibility to form a uniform solution, and no furtherevaluations were possible.

Comparative Example 4

An attempt was made to prepare a composition solution in the same manneras in Example 1 except that Resin solution i obtained in SynthesisExample 1 was replaced with a resin solution prepared by mixing Resinsolutions 12 and 13 obtained in Synthesis Examples 12 and 13 in a solidcontent mixing ratio of 1:1. However, Resin solutions 12 and 13 had toopoor compatibility to form a uniform solution, and no furtherevaluations were possible.

Comparative Example 5

A composition solution was prepared in the same manner as in Example 1except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25.0 g of EA-7180-1 (epoxy equivalent 655, acid value80.5, supplied by Shinnakamura Chemical Industrial Co., Ltd.) obtainedby carboxylating 50% acrylate of a cresol novolak type epoxy resin, andthe composition solution was treated and evaluated in the same manner asin Example 1.

Table 2 shows the results.

Comparative Example 6

A composition solution was prepared in the same manner as in Example 1except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25.0 g of EA-6540 (acid value 80, supplied by ShinnakamuraChemical Industrial Co.. Ltd.) obtained by carboxylating acrylate of aphenol novolak type epoxy resin, and the composition solution wastreated and evaluated In the same manner as in Example 1.

Table 2 shows the results.

Comparative Example 7

A composition solution was prepared in the same manner as in Example 1except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25.0 g of EA-1040 (acid value 80, supplied by ShinnakamuraChemical Industrial Co., Ltd.) obtained by carboxylating acrylate of abisphenol A type epoxy resin, and the composition solution was treatedand evaluated in the same manner as in Example 1.

Table 2 shows the results.

Comparative Example 8

A composition solution was prepared in the same manner as in Example 1except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25 g of a cresol novolak type epoxy resin (Araldite ECN1273, supplied by Ciba Geigy) and 2.5 g of DICY (dicyandiamide) as acuring agent component, and the composition solution was treated andevaluated in the same manner as in Example 1.

Table 2 shows the results.

Comparative Example 9

A composition solution was prepared in the same manner as in Example 1except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25 g of a cresol novolak type epoxy resin (Araldite ECN1273, supplied by Ciba Geigy) and 2.5 g of 2E4MZ-CN(2-Ethyl-4-methyl-3-cyanoethyl-imidazole) (supplied by Shikoku ChemicalsCorporation) as a curing agent component, and the composition solutionwas treated and evaluated in the same manner as in Example 1.

                                      TABLE 2                                     __________________________________________________________________________                          Resistance to                                           Comp.            Heat discoloration                                                                        Flattening                                                                          Adhesion                                                                           Storage                               Example                                                                            Hardness                                                                           Transparency                                                                         resistance                                                                         under heat                                                                           μm test stability                             __________________________________________________________________________    1    H    A      X    X      0.2<  B    A                                     2    H    A      X    X      0.3<  A    A                                     3    No uniform solution was formed and evaluation was impossible.            4    No uniform solution was formed and evaluation was impossible.            5    H    B      B    X      0.5<  A    B                                     6    H    B      B    X      0.5<  A    B                                     7    H    X      X    B      0.3<  A    B                                     8    3H   A      A    B      0.5<  B    X                                     9    3H   A      A    X      0.5<  A    X                                     __________________________________________________________________________

Example 12

(1) Preparation of radiation-sensitive resin composition

Aronix M-400 (supplied by Toagosei Chemical Industry Co., Inc.) in anamount of 120 parts by weight based on the resin content of Resinsolution 1 obtained in Synthesis Example 1 ("part by weight" is used inthis sense hereinafter in this Example), 20 parts by weight of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 10 parts byweight of γ-methacryloxypropyltrimethoxysilane and 0.1 part by weight ofSH-28PA were added to 100 g of Resin solution obtained in SynthesisExample 1, and these components were mixed. The mixture was filteredwith a 0.22 μm millipore filter to give a composition solution (2).

(2) Formation of coating

The above composition solution (2) was applied to an SiO₂ glasssubstrate with a spinner, and applied composition solution was pre-bakedon a hot plate at 80° C. for 5 minutes to give a coating having athickness of 2.0 μm.

(3) Evaluation of resist properties

The resist film obtained in the above (2) was exposed to light from ahigh-pressure mercury lamp (USH-250D, supplied by Ushio Inc.) at 200mJ/cm² (by means of 365 nm sensor) through a resolution-measuringnegative mask (TOPPAN-TEST-CHART-N) in oxygen atmosphere (in air). Then,the resist film was developed with an aqueous solution oftetramethylammonium hydroxide at 25° C. for 1 minute, rinsed withultrapure water for 1 minute and subjected to nitrogen blowing to aremaining pattern. The pattern was observed through an opticalmicroscope to measure a resolution. Further, after the development, thefilm thickness was measured (with α-step 100 supplied by HERZ) todetermine a film remaining ratio (%). The film remaining ratio refers toa value obtained by dividing the thickness of the developed film by thethickness of the pre-baked film and multiplying the quotient by 100. Theresist properties were evaluated as follows. When the film remainingratio was over 90%, a coating was rated as A. When it was 90 to 80%, acoating was evaluated as B. When it was less than 80%, a coating wasevaluated as X.

Table 3 shows the developer concentration (at which a non-exposedportion was removable), the resolution and the film remaining ratio.

(4) Curing of coating

The coating obtained in the above (3) was cured by heating it on a hotplate at 200° C. for 20 minutes.

(5) Evaluation of transparency

A coating was formed in the same manner as in the above (2) except thatthe SiO₂ glass substrate was replaced with a Corning 7059 (supplied byCorning).

The above-obtained coating was measured for a transmittance at 400 to800 nm with a spectrophotometer (model 150-20, double beam, supplied byHitachi Ltd.). The transparency was evaluated as follows. When thelowest transmittance was over 98%. a coating was rated as A. When it was95 to 98%, a coating was rated as B. When it was less than 95%, acoating was rated as X. Table 3 shows the result.

(6) Evaluation of heat resistance

A substrate on which a coating had been formed In the same manner as inthe above (2) was heated on a hot plate at 250° C. for 1 hour, and thenthe coating was measured for a thickness. Then, the film remaining ratioto the thickness of the coating before the heat treatment wascalculated. The heat resistance was evaluated as follows. When the filmremaining ratio was over 98%, a coating was rated as A. When it was 95to 98%, a coating was rated as B. When it was less than 95%, a coatingwas rated as X. Table 3 shows the result.

(7) Evaluation of resistance to discoloration under heat

A substrate on which a coating had been formed in the same manner as inthe above (2) was heated on a hot plate at 250° C. for 1 hour. Then, thecoating was measured for a transmittance with a spectrophotometer in thesame manner as in the above (3), and the change ratio to thetransmittance of the coating before the heat treatment was calculated.The resistance to discoloration under heat was evaluated as follows.When the change ratio was less than 5%, a coating was rated as A. Whenit was 5 to 10%, a coating was rated as B. When it was over 10%, acoating was rated as X. Table 3 shows the result.

(8) Measurement of hardness

The same coating as that prepared in the above (5) was measured for ahardness by a pencil scratch test according to JIS K-5400-1990, 8.4.1.The hardness was evaluated on the basis of scratch on the coating. Table3 shows the result.

(9) Evaluation of flattening

A coating was formed in the same manner as in the above (2)-(4) exceptthat the SiO₂ glass substrate was replaced with an SiO₂ wafer having aheight difference on the surface by 1.0 μm. Then, the substrate wasmeasured for a height difference on the surface with a tracer type filmthickness measuring apparatus. Table 3 shows the result.

(10) Storage stability

The composition solution (2) obtained in the above (1) was heated in aconstant-temperature constant-humidity device at 40° C. for 200 hours,and measured for a viscosity change. The storage stability was evaluatedas follows. When the viscosity change was less than 5%, a solution wasrated as A. When it was 5 to 10%, a solution was rated as B. When it wasover 10%, a solution was rated as X. Table 3 shows the result.

Examples 13-22

Composition solutions were prepared in the same manner as in Example 12except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with Resin solutions obtained in Synthesis Examples 2 to 11.The composition solutions were treated and evaluated in the same manneras in Example 12.

Table 3 shows the results.

Example 23

A composition solution was prepared in the same manner as in Example 12except that the2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one was replacedwith 2,4,6-trimethylbenzoyldlphenylphosphine oxide. The compositionsolution was treated and evaluated in the same manner as in Example 12.Table 3 shows the results.

Example 24

A composition solution was prepared in the same manner as in Example 12except that the2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one was replacedwith 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane. Thecomposition solution was treated and evaluated in the same manner as inExample 12. Table 3 shows the results.

Example 25

A composition solution was prepared in the same manner as in Example 12except that the Aronix M-400 (supplied by Toagosei Chemical IndustryCo., Inc.) was replaced with Aronix M-8060 (supplied by ToagoseiChemical Industry Co., Inc.). The composition solution was treated andevaluated in the same manner as in Example 12. Table 3 shows theresults.

Example 26

A composition solution was prepared in the same manner as in Example 12except that the Aronix M-400 (supplied by Toagosei Chemical IndustryCo., Inc.) was replaced with Aronix M-210 (supplied by Toagosei ChemicalIndustry Co., Inc.). The composition solution was treated and evaluatedin the same manner as in Example 12. Table 3 shows the results.

Example 27

A composition solution was prepared in the same manner as in Example 12except that the Aronix M-400 (supplied by Toagosei Chemical IndustryCo., Inc.) was replaced with KAYARAD TMPTA (supplied by Nippon KayakuCo., Ltd.). The composition solution was treated and evaluated in thesame manner as in Example 2. Table 3 shows the results.

                                      TABLE 3                                     __________________________________________________________________________         Concentration Film                 Resistance to                              of developer                                                                          Resolution                                                                          remaining  Trans-                                                                             Heat discoloration                                                                        Flattening                                                                          Adhesion                                                                           Storage             Example                                                                            solution wt %                                                                         μm ratio Hardness                                                                           parency                                                                            resistance                                                                         under heat                                                                           μm test stability           __________________________________________________________________________    12   0.14    14    A     5H   A    A    A      0.2>  A    A                   13   1.5     12    A     4H   A    A    A      0.2>  A    A                   14   0.20    10    A     5H   A    A    A      0.3>  A    A                   15   0.14    16    A     4H   A    A    A      0.3>  A    A                   16   1.0     16    A     4H   A    A    A      0.2>  A    A                   17   0.20    6.0   A     3H   A    A    A      0.1>  A    A                   18   1.6     2.0   A     4H   A    A    A      0.1>  A    A                   19   0.8     4.0   A     5H   A    A    A      0.1>  A    A                   20   0.5     1.8   A     6H   A    A    A      0.1>  A    A                   21   0.14    2.0   A     4H   A    A    A      0.1>  A    A                   22   0.4     4.2   A     5H   A    A    A      0.1>  A    A                   23   0.16    10    A     4H   A    A    A      0.1>  A    A                   24   0.14    12    A     4H   A    A    A      0.1>  A    A                   25   0.20    10    A     3H   A    A    A      0.1>  A    A                   26   0.16    14    A     4H   A    A    A      0.1>  A    A                   27   1.20    12    A     4H   A    A    A      0.1>  A    A                   __________________________________________________________________________

Comparative Example 10

A composition solution was prepared in the same manner as in Example 12except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25.0 g of EA-7130-1 (epoxy equivalent 655, acid value80.5, supplied by Shinnakamura Chemical Industrial Co., Ltd.) obtainedby carboxylating 50% acrylate of a cresol novolak type epoxy resin, andthe composition solution was treated and evaluated in the same manner asin Example 12.

Table 4 shows the results.

Comparative Example 11

A composition solution was prepared in the same manner as in Example 11except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25.0 g of EA-6540 (acid value 80, supplied by ShinnakamuraChemical Industrial Co., Ltd.) obtained by carboxylating acrylate of aphenol novolak type epoxy resin, and the composition solution wastreated and evaluated in the same manner as in Example 12.

Table 4 shows the results.

Comparative Example 12

A composition solution was prepared in the same manner as in Example 12except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25.0 g of EA-1040 (acid value 80, supplied by ShinnakamuraChemical Industrial Co., Ltd.) obtained by carboxylating acrylate of abisphenol A type epoxy resin, and the composition solution was treatedand evaluated in the same manner as in Example 12.

Table 2 shows the results.

Comparative Example 13

A composition solution was prepared in the same manner as in Example 12except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25 g of a cresol novolak type epoxy resin (Araldite ECN1273, supplied by Ciba Geigy) and 2.5 g of DICY (dicyandiamide) as acuring agent component, and the composition solution was treated andevaluated in the same manner as in Example 12.

Table 4 shows the results.

Comparative Example 14

A composition solution was prepared in the same manner as in Example 12except that Resin solution 1 obtained in Synthesis Example 1 wasreplaced with 25 g of a cresol novolak type epoxy resin (Araldite ECN1273, supplied by Ciba Geigy) and 2.5 g of 2E4MZ-CN (supplied by ShikokuChemicals Corporation) as a curing agent component, and the compositionsolution was treated and evaluated in the same manner as in Example 12.

Table 4 shows the results.

                                      TABLE 4                                     __________________________________________________________________________         Concentration Film                 Resistance to                         Comp.                                                                              of developer                                                                          Resolution                                                                          remaining  Trans-                                                                             Heat discoloration                                                                        Flattening                                                                          Adhesion                                                                           Storage             Example                                                                            solution wt %                                                                         μm ratio Hardness                                                                           parency                                                                            resistance                                                                         under heat                                                                           μm test stability           __________________________________________________________________________    10   1.6     30    B     2H   X    B    X      0.6<  A    B                   11   1.4     34    B      H   B    B    X      0.6<  A    B                   12   1.5     40    X     2H   B    B    B      0.5<  A    X                   13   Development                                                                           --    --    --   --   --   --     --    --   --                       impossible                                                               14   Development                                                                           --    --    --   --   --   --     --    --   --                       impossible                                                               __________________________________________________________________________

What is claimed is:
 1. An epoxy group-containing radiation-sensitiveresin composition comprising:(A) a copolymer obtained from the followingunsaturated monomers which comprise (a), (b) and (c):(a) 5 to 40% byweight of at least one member selected from the group consisting of anunsaturated carboxylic acid and an unsaturated carboxylic acidanhydride, (b) 10 to 70% by weight of an epoxy group containingunsaturated compound, and (c) 10 to 70% by weight of a monoolefinunsaturated compound selected from the group consisting of an alkylester, hydroxyalkyl ester, cycloalkyl ester or aryl ester of analiphatic unsaturated carboxylic acid, a dialkyl ester of an aliphaticunsaturated dicarboxylic acid, and styrene compounds, (B) an organicsolvent for dissolving the above copolymer, (C) a polymerizable compoundhaving at least one ethylenically unsaturated double bond, (D) aphotopolymerization initiator, and (E) a silane coupling agent.
 2. Thecomposition of claim 1, wherein the unsaturated carboxylic acid and theunsaturated carboxylic acid anhydride are selected from aliphatic mono-and dicarboxylic acids having 3 to 5 carbon atoms, anhydrides thereofand half esters of aliphatic dicarboxylic acids.
 3. The composition ofclaim 1, wherein the epoxy group-containing unsaturated compound is anepoxy alkyl ester of acrylic acid or α-alkylacrylic acid, andN-epoxyalkyl acrylamide or α-alkylacrylamide.
 4. The composition ofclaim 1, wherein the copolymer is contained in an amount of 3 to 50parts by weight when the total amount of the copolymer and the organicsolvent is 100 parts by weight.
 5. The composition as claimed in claim1, wherein said unsaturated carboxylic acid has the formula: ##STR14##and the unsaturated carboxylic acid anhydride has the formula: ##STR15##wherein R¹ and R² in both of the above formulae independently representa hydrogen atom or a C₁ -C₆ alkyl group.
 6. The composition as claimedin claim 5, wherein said epoxy group-containing unsaturated compound hasthe formula: ##STR16## wherein R³ is a hydrogen atom or a C₁ -C₄ alkylgroup, n is an integer of from 1 to 10, and X is --O-- or a group havingthe formula: ##STR17## wherein R¹ is a C₁ -C₆ alkyl group and m is aninteger of from 1 to
 10. 7. The composition as claimed in claim 6,wherein said monoolefin unsaturated compound has the formula: ##STR18##wherein R⁴ is a hydrogen atom or a C₁ -C₄ alkyl group and R⁵ is hydrogenatom, a C₁ -C₆ alkyl group or a C₁ -C₄ alkoxy group, or has the formula:##STR19## wherein each of R⁶ and R⁷ is independently a hydrogen atom ora methyl group and wherein R⁸ is a C₁ -C₆ alkyl group or a C₅ -C₁₂cycloalkyl group.
 8. The composition as claimed in claim 7, wherein saidcomponent (a) is selected from the group consisting of acrylic acid,methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconicacid, mesaconic acid, itaconic acid, maleic anhydride, itaconicanhydride, monomethyl fumarate, monobutyl fumarate, monomethyl maleate,monoethyl maleate, monobutyl maleate, monomethyl itaconate, monoethylitaconate and monobutyl itaconate,wherein said component (b) is selectedfrom the group consisting of glycidyl acrylate, glycidyl methacrylate,glycidyl α-n-butylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutylmethacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate,6,7-epoxyheptyl α-ethylacrylate,N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide andN-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, and whereinsaid component (C) is selected from the group consisting of methylmethacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butylmethacrylate, tert-butyl methacrylate, methyl acrylate, isopropylacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate,dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate,isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexylacrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate,isobornyl acrylate, phenyl methacrylate, benzyl methacrylate, phenylacrylate, benzyl acrylate, diethyl maleate, diethyl fumarate, diethylitaconate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene,vinyltoluene, p-methoxystyrene and p-tert-butoxystyrene.
 9. Thecomposition as claimed in claim 8, wherein said component (E) isselected from the group consisting of trimethoxysilylbenzoic acid,γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane,vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycylcohexyl)ethyltrimethoxysilane.
 10. The composition of claim 1, wherein the polymerizablecompound having at least one ethylenically unsaturated double bond ismonofunctional or polyfunctional ester of acrylic acid or methacrylicacid.
 11. The composition of claim 1, wherein the polymerizable compoundhaving at least one ethylenically unsaturated double bond is containedin an amount of 40 to 200 parts by weight and the photopolymerizationinitiator is contained in an amount of 1 to 50 parts by weight, per 100parts by weight of the copolymer (A).
 12. The composition as claimed inclaim 1, wherein said copolymer (A) is obtained from said unsaturatedmonomers which consist of (a), (b) and (c).
 13. The composition asclaimed in claim 1, wherein said component (E) is selected from thegroup consisting of trimethoxysilylbenzoic acid,γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane,vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycylcohexyl)ethyltrimethoxysilane.
 14. An epoxy group-containing radiation-sensitive resincomposition comprising:(A)' a copolymer obtained from the followingunsaturated monomers which comprise (a), (b), (c) and (d):(a) 5 to 40%by weight of at least one member selected from the group consisting ofan unsaturated carboxylic acid and an unsaturated carboxylic acidanhydride, (b) 10 to 70% by weight of an epoxy group-containingunsaturated compound, (c) 10 to 70% by weight of a monoolefinunsaturated compound selected from the group consisting of an alkylester, hydroxyalkyl ester, cycloalkyl ester or aryl ester of analiphatic unsaturated carboxylic acid, a dialkyl ester of an aliphaticunsaturated dicarboxylic acid, and styrene compounds, and (d) 0.1 to 30%by weight of structural units derived from a conjugated diolefinunsaturated compound, (B) an organic solvent for dissolving the abovecopolymer, (C) a polymerizable compound having at least oneethylenically unsaturated double bond, (D) a photopolymerizationinitiator, and (E) a silane coupling agent.
 15. The composition of claim14, wherein the unsaturated carboxylic acid and the unsaturatedcarboxylic acid anhydride are selected from aliphatic mono- anddicarboxylic acids having 3 to 5 carbon atoms, anhydrides thereof andhalf esters of aliphatic dicarboxylic acids.
 16. The composition ofclaim 14, wherein the epoxy group-containing unsaturated compound is anepoxy alkyl ester of acrylic acid or α-alkylacrylic acid, andN-epoxyalkyl acrylamide or α-alkylacrylamide.
 17. The composition ofclaim 14, wherein the copolymer is contained in an amount of 3 to 50parts by weight when the total amount of the copolymer and the organicsolvent is 100 parts by weight.
 18. The composition as claimed in claim14, wherein said unsaturated carboxylic acid has the formula: ##STR20##and the unsaturated carboxylic acid anhydride has the formula: ##STR21##wherein R¹ and R² in both of the above formulae independently representa hydrogen atom or a C₁ -C₆ alkyl group.
 19. The composition as claimedin claim 18, wherein said epoxy group-containing unsaturated compoundhas the formula: ##STR22## wherein R³ is a hydrogen atom or a C₁ -C₄alkyl group, n is an integer of from 1 to 10, and X is --O-- or a grouphaving the formula: ##STR23## wherein R¹ is a C₁ -C₆ alkyl group and mis an integer of from 1 to
 10. 20. The composition as claimed in claim19, wherein said monoolefin unsaturated compound has the formula:##STR24## wherein R⁴ is a hydrogen atom or a C₁ -C₄ alkyl group and R⁵is hydrogen atom, a C₁ -C₆ alkyl group or a C₁ -C₄ alkoxy group, or hasthe formula: ##STR25## wherein each of R⁶ and R⁷ is independently ahydrogen atom or a methyl group and wherein R⁸ is a C₁ -C₆ alkyl groupor a C₅ -C₁₂ cycloalkyl group.
 21. The composition of claim 20, whereinthe conjugated diolefin unsaturated compound has the formula ##STR26##wherein each of R⁹ and R¹⁰ is independently a hydrogen atom, a methylgroup or an optionally substituted phenyl group.
 22. The composition asclaimed in claim 21, wherein said component (a) is selected from thegroup consisting of acrylic acid, methacrylic acid, crotonic acid,maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconicacid, maleic anhydride, itaconic anhydride, monomethyl fumarate,monobutyl fumarate, monomethyl maleate, monoethyl maleate, monobutylmaleate, monomethyl itaconate, monoethyl itaconate and monobutylitaconate,wherein said component (b) is selected from the groupconsisting of glycidyl acrylate, glycidyl methacrylate, glycidylα-n-butylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate,6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptylα-ethylacrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamideand N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, whereinsaid component (C) is selected from the group consisting of methylmethacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butylmethacrylate, tert-butyl methacrylate, methyl acrylate, isopropylacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate,dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate,isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexylacrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate,isobornyl acrylate, phenyl methacrylate, benzyl methacrylate, phenylacrylate, benzyl acrylate, diethyl maleate, diethyl fumarate, diethylitaconate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,styrene, α-methylstyrene, methylstyrene, p-methylstyrene, vinyltoluene,p-methoxystyrene and p-tert-butoxystyrene, and wherein said component(d) is selected from the group consisting of 1,3-butadiene,2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and2-phenyl-l,3-butadiene.
 23. The composition as claimed in claim 22,wherein said component (E) is selected from the group consisting oftrimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane,vinyltriacetoxysilane, vinyltrimethoxysilane,γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane andβ-(3,4-epoxycylcohexyl)ethyltri methoxysilane.
 24. The composition ofclaim 14, wherein the polymerizable compound having at least oneethylenically unsaturated double bond is monofunctional orpolyfunctional ester of acrylic acid or methacrylic acid.
 25. Thecomposition of claim 14, wherein the polymerizable compound having atleast one ethylenically unsaturated double bond is contained in anamount of 40 to 200 parts by weight and the photopolymerizationinitiator is contained in an amount of i to 50 parts by weight, per 100parts by weight of the copolymer (A).
 26. The composition as claimed inclaim 14, wherein said copolymer (A)' is obtained from said unsaturatedmonomers which consist of (a), (b), (c) and (d).
 27. The composition asclaimed in claim 14, wherein said component (E) is selected from thegroup consisting of trimethoxysilylbenzoic acid,γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane,vinyltrimethoxysilane, silane, γ-isocyanatopropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycylcohexyl)ethyltrimethoxysilane.